title: Formic and acetic acid aggregation in the liquid state.
abstract: The microscopic structure of neat formic and acetic acid have been measured by neutron diffraction with H/D substitution on SANDALS at the ISIS neutron spallation source. These data, together with complementary x-ray data, have been modeled via the empirical potential structure refinement (EPSR) method, which integrates information obtained from the diffraction data in a Monte Carlo simulation in order to provide a three-dimensional model of the system under study compatible with the measured structure factors. Two models have been generated for each acid, in order to test their consistency, with positive results. The final structure obtained is that of two liquids that are very similar to each other, with high connectivity although rather disordered. They present a hierarchy of probability for hydrogen bond formation, where weaker bonds involving the carbonyl hydrogen for formic acid or the methyl hydrogen for acetic acid are more abundant than the stronger bonds involving the hydroxyl hydrogen. Cooperative effects are found to be fundamental for the description of aggregation of formic and acetic acid, but the structure in the liquid presents a greater variety of bonds than in the solid state.
authors.affiliation: STFC, ISIS facility, Rutherford Appleton Laboratory, Didcot, OX11 0QX, UK. silvia.imberti@stfc.ac.uk
authors.forename: Silvia
authors.initials: S
authors.lastname: Imberti
authors.forename: Daniel T
authors.initials: DT
authors.lastname: Bowron
mesh_terms: D019342:Acetic Acid / Q000737:chemistry*; D003198:Computer Simulation; D005561:Formates / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D009010:Monte Carlo Method; D012997:Solvents / Q000737:chemistry*
chemical_list: D005561:Formates; D012997:Solvents; C030544:formic acid; D019342:Acetic Acid